CN115893749A - Resource utilization method for lithium battery anode ternary precursor production wastewater - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 239000002243 precursor Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 54
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 52
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 52
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 36
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 35
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 29
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 27
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 27
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 26
- 239000012452 mother liquor Substances 0.000 claims abstract description 26
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 24
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 230000008014 freezing Effects 0.000 claims abstract description 8
- 238000007710 freezing Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A resource utilization method for lithium battery anode ternary precursor production wastewater comprises the following steps: (1) concentrating the wastewater, adding sodium carbonate, and taking clear liquid; adding ammonium bicarbonate to react, and performing solid-liquid separation to obtain sodium bicarbonate precipitate and ammonium sulfate mother liquor; (2) Adjusting the ammonium sulfate mother liquor to acidity with sulfuric acid, concentrating, freezing and crystallizing, and carrying out solid-liquid separation to obtain sodium sulfate crystals and an ammonium sulfate solution; (3) And evaporating and crystallizing the ammonium sulfate solution to obtain an ammonium sulfate product. The nitrogen content of the obtained ammonium sulfate product is more than 20.5 percent, and the requirement of GB535 is met; the by-product sodium sulfate can be recycled, and the utilization rate of the sodium sulfate can reach more than 90 percent; simultaneously, a high-purity sodium bicarbonate product is obtained; the method has the advantages of simple process, convenient operation, less energy consumption, low reactant cost and easy obtainment, and the obtained products of ammonium bicarbonate and ammonium sulfate have large market demand and are wholly economically feasible.
Description
Technical Field
The invention relates to a resource utilization method of wastewater, in particular to a resource utilization method of anode ternary precursor production wastewater.
Background
Sodium sulfate (Na) 2 SO 4 ) It is white, odorless and bitter crystal powder, has hygroscopicity, and can be used for producing sodium sulfate decahydrate (Natrii sulfas) by absorbing water when exposed to air, and is alkaline, and is mainly used for producing water glass, enamel, paper pulp, refrigerating mixture, detergent, desiccant, dye diluent, analytical chemical, medicinal products, feed, etc.
Under the policy background, with the rapid development of the new energy automobile industry, the installed capacity of the lithium ion battery at the upstream of the industry chain is greatly increased, but a large amount of Na is produced in the process of producing the lithium ion battery 2 SO 4 A by-product. For example, in the process of producing precursors of power batteries, NH is often added into the solution to obtain precursors with qualified performance 3 And NaOH, wherein NH 3 Often as a complexing agent for metal ions in solution, and NaOH as a precipitant for metal ions in solution, the typical reaction process is as follows: meSO 4 ▪xH 2 O+xNH 3 +2NaOH=Me(OH) 2 ↓+Na 2 SO 4 +xNH 3 ▪H 2 O, resulting in a large amount of Na in the filtrate after synthesis of the precursor 2 SO 4 And NH 3 ▪H 2 And (O). The main process for treating the wastewater at present is to recover ammonia by evaporation, concentrate, freeze, crystallize and separate out Na 2 SO 4 ▪10H 2 And (O). Data show that with the production of lithium batteries, about 130 million tons of anhydrous sodium sulfate are generated in China every year, and the byproduct sodium sulfate is increased year by year along with the increase of the usage amount of power batteries. Therefore, the synthesis waste of the precursor of the positive electrode material of the power battery is strengthenedThe resource utilization of the sodium sulfate in water is urgent and important.
CN 112875726A discloses a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate, which comprises the steps of adding soluble calcium salt into mother liquor after double decomposition reaction, combining with sulfate radical to generate calcium sulfate precipitate, adding quicklime into the solution after precipitation to remove ammonium ions, and introducing carbon dioxide as calcium salt solution for recycling. The method has long process flow and complex operation process, and has high heating temperature, large energy consumption, high cost and difficult industrialization when preparing calcium sulfate dihydrate products and treating waste liquid.
CN 1761617A discloses a method of separating sodium sulfate and ammonium sulfate from mother liquor after metathesis reaction by cooling-evaporation method. The optimal cooling temperature of the mother liquor provided by the method is-5 ℃ to-2 ℃, sodium sulfate crystals are separated out, the ratio of sodium sulfate to ammonium sulfate in the mother liquor is close to 1. The method has the advantages of low utilization rate of sulfate radicals, low purity of the obtained product, large material circulation amount and high production and operation cost.
CN 104355326A discloses a method for preparing sodium bicarbonate and ammonium sulfate by double decomposition, in which sodium bicarbonate is prepared by double decomposition reaction of sodium sulfate and ammonium bicarbonate, carbonate and bicarbonate are converted into carbon dioxide by a mother liquor after solid-liquid separation at high temperature, sodium sulfate crystals are obtained by evaporation and recycled to the double decomposition reaction, the separated mother liquor is cooled and crystallized to obtain double salts of sodium sulfate and ammonium sulfate, and the mother liquor is evaporated and crystallized to obtain ammonium sulfate products. The method has the advantages of more high-temperature heating processes, higher energy consumption, higher cost and low utilization rate of raw materials.
CN 111039310A discloses a method for preparing sodium bicarbonate and co-producing ammonium sulfate from sodium sulfate, which comprises the steps of adding an accelerant during double decomposition reaction of sodium sulfate and ammonium bicarbonate, performing solid-liquid separation, and recovering an ammonium bicarbonate raw material through flash evaporation, so that the conversion rate of sodium sulfate and the nitrogen content of ammonium sulfate are improved, but the purity of the prepared sodium bicarbonate product is low, the introduced accelerant and the flash evaporation operation increase the cost, and the method is not suitable for industrial processes of large-scale treatment in factories.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provide a resource utilization method of lithium battery anode ternary precursor production wastewater, which has high comprehensive utilization rate of raw materials and high product purity.
The technical scheme adopted by the invention for solving the technical problem is as follows: a resource utilization method of lithium battery anode ternary precursor production wastewater comprises the following steps:
(1) Concentrating the wastewater, adding sodium carbonate, and taking clear liquid; adding ammonium bicarbonate to react, and carrying out solid-liquid separation to obtain sodium bicarbonate precipitate and ammonium sulfate mother liquor; after the sodium carbonate is added, the precipitation of elements such as magnesium and the like can be generated; the obtained sodium bicarbonate precipitate is washed and dried conventionally to obtain a sodium bicarbonate product;
(2) Adjusting the ammonium sulfate mother liquor to acidity with sulfuric acid, concentrating, freezing and crystallizing, and carrying out solid-liquid separation to obtain sodium sulfate crystals and an ammonium sulfate solution;
(3) And evaporating and crystallizing the ammonium sulfate solution to obtain an ammonium sulfate product.
In the step (1), sodium carbonate is added by adding a saturated sodium carbonate solution until the pH value of the wastewater is adjusted to be more than 8.5.
In the step (1), na in the clear liquid 2 SO 4 The concentration is 250 g/L-400 g/L.
In the step (1), the molar ratio of sodium ions to ammonium bicarbonate in the clear liquid is 1:0.9 to 1.1.
In the step (1), the reaction temperature is 36-40 ℃, and the reaction time is 1-4 h.
In the step (2), the ammonium sulfate mother liquor is adjusted to pH =3.5 to 5 with sulfuric acid.
And (3) concentrating until the volume is reduced by 40 to 60 percent in the step (2).
In step (2), concentration is carried out by evaporation.
In the step (2), the evaporation temperature is 70-100 ℃.
In the step (2), the temperature of freezing crystallization is-12 to-10 ℃.
The sodium sulfate in the mother liquor is separated out under the temperature condition, so that a purer ammonium sulfate solution can be obtained, the material circulation amount is reduced, the cyclic utilization rate of the sodium sulfate is improved, and the purities of the obtained sodium bicarbonate and the ammonium sulfate are high.
And (3) adding the sodium sulfate crystals obtained in the step (2) into next batch of wastewater or clear liquid to react with ammonium bicarbonate.
The method takes the synthetic wastewater of the precursor of the anode material of the power battery as the raw material, adds the solid ammonium bicarbonate after pretreatment, and separates out the sodium bicarbonate by utilizing the homoionic effect. The ammonium sulfate mother liquor is crystallized in multiple steps, the precipitated sodium sulfate is recycled, and the nitrogen content of the ammonium sulfate product can meet the requirement of GB 535.
In the step (1) of the invention, the double decomposition reaction of sodium carbonate and ammonium bicarbonate in the wastewater comprises the following steps:
Na 2 SO 4 +2NH 4 HCO 3 → 2NaHCO 3 ↓+(NH 4 ) 2 SO 4 （1）
in the step (2), after the sulfuric acid is added into the mother liquor, the sulfuric acid and a small amount of ammonium bicarbonate or ammonium carbonate in the mother liquor can continuously form ammonium sulfate:
H 2 SO 4 +2NH 4 HCO 3 → 2CO 2 ↑+(NH 4 ) 2 SO 4 +2H 2 O （2）
H 2 SO 4 +(NH 4 ) 2 CO 3 → CO 2 ↑+(NH 4 ) 2 SO 4 +H 2 O （3）
after the addition of sulfuric acid, if heated, the mother liquor can be further removed of carbonate or bicarbonate to obtain a high purity product:
NH 4 HCO 3 ≜CO 2 ↑+NH 3 ↑+H 2 O （4）
(NH 4 ) 2 CO 3 ≜CO 2 ↑+2NH 3 ↑+H 2 O （5）
the invention has the beneficial effects that:
(1) The nitrogen content of the ammonium sulfate product is more than 20.5 percent, and the requirement of GB535 is met; the by-product sodium sulfate can be recycled, and the utilization rate of the sodium sulfate can reach more than 90 percent; simultaneously, a high-purity sodium bicarbonate product is obtained;
(2) The process is simple, the operation is convenient, the energy consumption is less, and the sodium sulfate-containing wastewater can be converted and utilized to prepare sodium bicarbonate and ammonium sulfate;
(3) The method has the advantages of low cost and easy obtainment of reactants, large market demand of the obtained products of ammonium bicarbonate and ammonium sulfate, and economic feasibility of the whole method.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
The starting materials used in the examples of the present invention were all obtained from conventional commercial sources.
Example 1
The resource utilization method of the lithium battery anode ternary precursor production wastewater comprises the following steps:
(1) Evaporating and concentrating waste liquid obtained by filtering a ternary precursor for producing the lithium battery anode, adding a saturated sodium carbonate solution to adjust the pH value to 9, filtering and taking clear liquid, wherein the clear liquid contains 300g/L Na 2 SO 4 (ii) a Adding ammonium bicarbonate under the stirring condition to carry out double decomposition reaction, wherein the molar ratio of sodium ions in clear liquid to the ammonium bicarbonate is 1.1, the reaction temperature is 36 ℃, and the reaction time is 2.5h; filtering to obtain sodium bicarbonate precipitate and ammonium sulfate mother liquor;
(2) Adjusting pH of the ammonium sulfate mother liquor to 4 with sulfuric acid, evaporating at 80 deg.C, concentrating, crystallizing to separate out sodium sulfate crystals (volume reduced by 40%), separating out the separated crystals, and freezing at-12 deg.C for crystallization to obtain small amount of sodium sulfate crystals and ammonium sulfate solution;
(3) And evaporating and crystallizing the ammonium sulfate solution to obtain an ammonium sulfate product.
The obtained ammonium sulfate product has the nitrogen content of 20.88 percent and the free acid content of less than 0.05 percent, and meets the requirement of GB/T535-2020.
And (2) carrying out conventional washing and drying on the sodium bicarbonate precipitate obtained in the step (1) to obtain a sodium bicarbonate product, wherein the purity of the sodium bicarbonate product is 99.8%.
And (3) adding the sodium sulfate crystals separated out in the step (2) into next batch of wastewater or clear liquid to participate in the double decomposition reaction of ammonium bicarbonate.
Example 2
The resource utilization method of the lithium battery anode ternary precursor production wastewater comprises the following steps:
(1) Evaporating and concentrating waste liquid obtained by filtering a ternary precursor for producing the lithium battery anode, adding a saturated sodium carbonate solution to adjust the pH value to 9, filtering to obtain clear liquid, wherein the clear liquid contains 350g/L Na 2 SO 4 Adding ammonium bicarbonate under the stirring condition to carry out double decomposition reaction, wherein the molar ratio of sodium ions in clear liquid to the ammonium bicarbonate is 1, the reaction temperature is 36 ℃, and the reaction time is 2.5 hours; filtering to obtain sodium bicarbonate precipitate and ammonium sulfate mother liquor;
(2) Adjusting pH of the ammonium sulfate mother liquor to 3.5 with sulfuric acid, evaporating, concentrating and crystallizing at 90 deg.C (volume reduced by 45%), and freezing and crystallizing at-12 deg.C to obtain sodium sulfate crystal and ammonium sulfate solution;
(3) And evaporating and crystallizing the ammonium sulfate solution to obtain an ammonium sulfate product.
The obtained ammonium sulfate product has the nitrogen content of 20.69 percent and the free acid content of less than 0.05 percent, and meets the requirement of GB/T535-2020.
And (2) carrying out conventional washing and drying on the sodium bicarbonate precipitate obtained in the step (1) to obtain a sodium bicarbonate product, wherein the purity of the sodium bicarbonate product is 99.55%.
And (3) adding the sodium sulfate crystals separated out in the step (2) into next batch of wastewater or clear liquid to participate in double decomposition reaction with ammonium bicarbonate.
Example 3
The resource utilization method of the lithium battery anode ternary precursor production wastewater comprises the following steps:
(1) Will produce the positive pole three of the lithium batteryEvaporating and concentrating the waste liquid obtained by filtering the precursor, adding saturated sodium carbonate solution to adjust the pH value to 9, filtering and taking clear liquid, wherein the clear liquid contains 300g/L Na 2 SO 4 Adding sodium sulfate crystal obtained from previous production to obtain Na 2 SO 4 The concentration is 350g/L; adding ammonium bicarbonate under the stirring condition to carry out double decomposition reaction, wherein the molar ratio of sodium ions in clear liquid to the ammonium bicarbonate is 1.1, the reaction temperature is 36 ℃, the reaction time is 2 hours, and filtering to obtain sodium bicarbonate sediment and ammonium sulfate mother liquor;
(2) Adjusting pH of the ammonium sulfate mother liquor to 4 with sulfuric acid, evaporating and concentrating at 80 deg.C (volume reduced by 60%) to crystallize and separate out sodium sulfate crystal, separating out crystal, and freezing at-12 deg.C for crystallization to obtain small amount of sodium sulfate crystal and ammonium sulfate solution;
(3) And evaporating and crystallizing the ammonium sulfate solution to obtain an ammonium sulfate product.
The obtained ammonium sulfate product has the nitrogen content of 21.0 percent and the free acid content of less than 0.05 percent, and meets the requirements of GB/T535-2020.
And (2) carrying out conventional washing and drying on the sodium bicarbonate precipitate obtained in the step (1) to obtain a sodium bicarbonate product, wherein the purity of the sodium bicarbonate product is 99.6%.
And (3) adding the sodium sulfate crystals separated out in the step (2) into next batch of wastewater or clear liquid to participate in the double decomposition reaction with ammonium bicarbonate.
The technical solutions of the present invention are clearly and completely described above in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Claims (10)
1. A resource utilization method for lithium battery anode ternary precursor production wastewater is characterized by comprising the following steps:
(1) Concentrating the wastewater, adding sodium carbonate, and taking clear liquid; adding ammonium bicarbonate to react, and carrying out solid-liquid separation to obtain sodium bicarbonate precipitate and ammonium sulfate mother liquor;
(2) Adjusting the ammonium sulfate mother liquor to acidity with sulfuric acid, concentrating, freezing and crystallizing, and carrying out solid-liquid separation to obtain sodium sulfate crystals and an ammonium sulfate solution;
(3) And evaporating and crystallizing the ammonium sulfate solution to obtain an ammonium sulfate product.
2. The resource utilization method of the lithium battery positive electrode ternary precursor production wastewater according to claim 1, characterized in that in the step (1), sodium carbonate is added by adding a saturated sodium carbonate solution until the pH value of the wastewater is adjusted to be more than 8.5.
3. The resource utilization method of lithium battery positive electrode ternary precursor production wastewater according to claim 1 or 2, characterized in that in step (1), na in the clear solution 2 SO 4 The concentration is 250 g/L-400 g/L.
4. The resource utilization method of the production wastewater of the lithium battery positive electrode ternary precursor of any one of claims 1 to 3, wherein in the step (1), the molar ratio of sodium ions to ammonium bicarbonate in the clear solution is 1:0.9 to 1.1.
5. The resource utilization method of the production wastewater of the lithium battery cathode ternary precursor according to any one of claims 1 to 4, characterized in that in the step (1), the reaction temperature is 36-40 ℃, and the reaction time is 1-4 h.
6. The resource utilization method of the lithium battery positive electrode ternary precursor production wastewater according to any one of claims 1 to 5, characterized in that in the step (2), the ammonium sulfate mother liquor is adjusted to pH = 3.5-5 with sulfuric acid.
7. The resource utilization method of the production wastewater of the lithium battery positive electrode ternary precursor according to any one of claims 1 to 6, characterized in that in the step (2), the concentration is carried out until the volume is reduced by 40 to 60%; concentration was performed by evaporation.
8. The resource utilization method of the lithium battery anode ternary precursor production wastewater according to claim 7, characterized in that in the step (2), the evaporation temperature is 70-100 ℃.
9. The resource utilization method of the lithium battery positive electrode ternary precursor production wastewater according to any one of claims 1 to 8, wherein in the step (2), the temperature of the freezing crystallization is-12 to-10 ℃.
10. The resource utilization method of lithium battery positive electrode ternary precursor production wastewater according to any one of claims 1 to 9, characterized in that the sodium sulfate crystals obtained in step (2) are added into next batch of wastewater or clear liquid to react with ammonium bicarbonate.
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| CN116835833A (en) * | 2023-08-24 | 2023-10-03 | 赛恩斯环保股份有限公司 | Resource utilization method of heavy metal sodium sulfate-containing wastewater |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1136348A (en) * | 1954-09-08 | 1957-05-13 | Chemie Linz Ag | Process for obtaining solid ammonium sulfate from aqueous solutions of ammonium sulfate |
| US5618511A (en) * | 1995-08-11 | 1997-04-08 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Process for producing ammonium sulfate from flue-gas scrubber waste liquor |
| US20190062188A1 (en) * | 2017-08-28 | 2019-02-28 | China Petroleum & Chemical Corporation | Apparatus and Method for Treating Waste Water Containing Ammonium Salts |
| CN113493214A (en) * | 2020-04-08 | 2021-10-12 | 郑州奥罗拉环保科技有限公司 | Novel method for preparing sodium bicarbonate and co-producing ammonium sulfate from sodium sulfate |
| CN113896219A (en) * | 2021-12-09 | 2022-01-07 | 中国科学院过程工程研究所 | Method for preparing sodium bicarbonate and byproducts ammonium sulfate and calcium carbonate from glauber salt |
| CN216808418U (en) * | 2022-01-28 | 2022-06-24 | 南京万德斯环保科技股份有限公司 | Sodium sulfate waste water resourceful treatment system |
| CN115010149A (en) * | 2022-07-12 | 2022-09-06 | 郑州中科新兴产业技术研究院 | Method for recycling sodium sulfate and ammonium sulfate from mixed salt |
-
2022
- 2022-12-19 CN CN202211631543.4A patent/CN115893749A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1136348A (en) * | 1954-09-08 | 1957-05-13 | Chemie Linz Ag | Process for obtaining solid ammonium sulfate from aqueous solutions of ammonium sulfate |
| US5618511A (en) * | 1995-08-11 | 1997-04-08 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Process for producing ammonium sulfate from flue-gas scrubber waste liquor |
| US20190062188A1 (en) * | 2017-08-28 | 2019-02-28 | China Petroleum & Chemical Corporation | Apparatus and Method for Treating Waste Water Containing Ammonium Salts |
| CN113493214A (en) * | 2020-04-08 | 2021-10-12 | 郑州奥罗拉环保科技有限公司 | Novel method for preparing sodium bicarbonate and co-producing ammonium sulfate from sodium sulfate |
| CN113896219A (en) * | 2021-12-09 | 2022-01-07 | 中国科学院过程工程研究所 | Method for preparing sodium bicarbonate and byproducts ammonium sulfate and calcium carbonate from glauber salt |
| CN216808418U (en) * | 2022-01-28 | 2022-06-24 | 南京万德斯环保科技股份有限公司 | Sodium sulfate waste water resourceful treatment system |
| CN115010149A (en) * | 2022-07-12 | 2022-09-06 | 郑州中科新兴产业技术研究院 | Method for recycling sodium sulfate and ammonium sulfate from mixed salt |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116835833A (en) * | 2023-08-24 | 2023-10-03 | 赛恩斯环保股份有限公司 | Resource utilization method of heavy metal sodium sulfate-containing wastewater |
| CN116835833B (en) * | 2023-08-24 | 2023-12-22 | 赛恩斯环保股份有限公司 | Resource utilization method of heavy metal sodium sulfate-containing wastewater |
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